Dakin Oxidation

177

Dakin oxidation

Oxidation of aryl aldehydes or aryl ketones to phenols using basic hydrogen per-oxide conditions. Cf. BaeyerVilliger oxidation.

HO CHOH2O2, NaOH

4550 oCHO OH HCO2H

O O H

HOH

OHO

OH

O

HO

aryl

migration

OHO

H OHOhydrolysisHO O

HO

OH

HO2CH HO OHHO O CHO2

Example 16

OBnCHO

NHCO2t-Bu

CO2H

2.5 eq. 30% H2O2

4% (PhSe)2, CH2Cl2, 18 h

OBnO

NHCO2t-Bu

CO2H

CHONH3, MeOH, 1 h

78%

OBnOH

NHCO2t-Bu

CO2H

178

Example 27

HO

CHO urea-hydrogen peroxide (UHP)

solvent-free, 55 oC, 3 h, 83% HO

OH

References:

1. Dakin, H. D. J. Am. Chem. Soc. 1909, 42, 477. Henry D. Dakin (18801952) was born in London, England. During WWI, he invented his hypochlorite solution (Da-kins solution), which became a popular antiseptic for the treatment of wounds. After the Great War, he emmigrated to New York, where he investigated the B vitamins.

2. Hocking, M. B.; Bhandari, K.; Shell, B.; Smyth, T. A. J. Org. Chem. 1982, 47, 4208. 3. Matsumoto, M.; Kobayashi, H.; Hotta, Y. J. Org. Chem. 1984, 49, 4740. 4. Zhu, J.; Beugelmans, R.; Bigot, A.; Singh, G. P.; Bois-Choussy, M. Tetrahedron Lett.

1993, 34, 7401. 5. Guzmn, J. A.; Mendoza, V.; Garca, E.; Garibay, C. F.; Olivares, L. Z.; Maldonado,

L. A. Synth. Commun. 1995, 25, 2121. 6. Jung, M. E.; Lazarova, T. I. J. Org. Chem. 1997, 62, 1553. 7. Varma, R. S.; Naicker, K. P. Org. Lett. 1999, 1, 189. 8. Roy, A.; Reddy, K. R.; Mohanta, P. K.; Ila, H.; Junjappa, H. Synth. Commun. 1999,

29, 3781. 9. Lawrence, N. J.; Rennison, D.; Woo, M.; McGown, A. T.; Hadfield, J. A. Bioorg.

Med. Chem. Lett. 2001, 11, 51.